Methods and systems for barrier layer surface passivation

ABSTRACT

This invention pertains to methods and systems for fabricating semiconductor devices. One aspect of the present invention is a method of depositing a gapfill copper layer onto barrier layer for semiconductor device metallization. In one embodiment, the method includes forming the barrier layer on a surface of a substrate and subjecting the barrier layer to a process condition so as to form a removable passivated surface on the barrier layer. The method further includes removing the passivated surface from the barrier layer and depositing the gapfill copper layer onto the barrier layer. Another aspect of the present invention is an integrated system for depositing a copper layer onto a barrier layer for semiconductor device metallization. In one embodiment, the integrated system comprises at least one process module configured for barrier layer deposition and passivated surface formation and at least one other process module configured for passivated surface removal and deposition of copper onto the barrier layer. The system further includes at least one transfer module coupled so that the substrate can be transferred between the modules substantially without exposure to an oxide-forming environment.

CROSS-REFERENCE

The present application is related to U.S. patent application Docket #XCR-002, titled “METHODS AND SYSTEMS FOR LOW INTERFACIAL OXIDE CONTACTBETWEEN BARRIER AND COPPER METALLIZATION,” to Fritz REDEKER, John BOYD,Yezdi DORDI, Alex YOON, and Shijian LI, filed Dec. 18, 2006; U.S. patentapplication Ser. No. 11/382,906, filed May 25, 2006; U.S. patentapplication Ser. No. 11/427,266, filed Jun. 28, 2006; U.S. patentapplication Ser. No. 11/461,415, filed Jul. 27, 2006; U.S. patentapplication Ser. No. 11/514,038, filed Aug. 30, 2006; U.S. patentapplication Ser. No. 10/357,664, filed Feb. 3, 2003; U.S. patentapplication Ser. No. 10/879,263, filed Jun. 28, 2004; and U.S. patentapplication Ser. No. 10/607,611, filed Jun. 27, 2003; all of thesepatents and/or applications are incorporated herein, in their entirety,by this reference.

BACKGROUND

This invention relates to improved methods and systems for themetallization of semiconductor devices such as integrated circuits,memory cells, and the like that use copper metallization; morespecifically this invention relates to methods and systems forcopper-based metallization of silicon integrated circuits.

An important part of the fabrication of semiconductor devices is themetallization of the devices to electrically interconnect the deviceelements. For many such devices, the metallization of choice includesthe use of copper metal lines. Metallization systems that use coppermetal lines also must use a barrier material to isolate the copper fromcopper sensitive areas of the electronic devices. Some of the barrierlayers of interest for copper metallization are materials such astantalum and such as tantalum nitride. The usual fabrication process formetallization systems that use copper involves the deposition of copperonto the barrier layers. A preferred process for depositing the copperonto the barrier layer is electroless copper deposition.

One problem that occurs for the standard technology used for coppermetallization is that many of the preferred barrier materials such astantalum and tantalum nitride, if exposed to air for extended periods oftime, can form oxides such as tantalum oxide and tantalum oxynitride onthe surface of the barrier layer. It is known that electrolessdeposition of copper onto the barrier layer is inhibited if there isoxide present on the barrier layer. In addition, copper does not adhereto the oxide on the barrier layer as well as it adheres to the purebarrier metal or metal rich barrier layer surface, such as tantalum andtantalum-rich surface on tantalum nitride. Tantalum and/or tantalumnitride barrier layers are only presented here as examples; similarproblems occur for other barrier layer materials. The poor adhesion cannegatively affect the electro-migration performance and reliability ofthe semiconductor devices. In addition, the formation of tantalum oxideor tantalum oxynitride on the barrier layer surface can increase theresistivity of the barrier layer. More specifically, the presence of theoxide between the barrier layer and the composite copper can reduce theperformance for the electronic devices and reduce the reliability of theelectronic devices fabricated using standard copper metallizationtechnology.

Clearly, there are numerous applications requiring high-performance highreliability electronic devices. The problems that occur for the standardtechnology for fabricating electronic devices using copper metallizationindicate there is a need for methods and systems that can allow thefabrication of electronic devices using copper metallization withimproved performance and improved reliability.

SUMMARY

This invention pertains to methods and systems for fabricatingsemiconductor devices. The present invention seeks to overcome one ormore of the deficiencies of the standard technologies for fabricatingsemiconductor devices such as integrated circuits, memory cells, and thelike that use copper metallization.

One aspect of the present invention is a method of depositing a gapfillcopper layer onto a transition metal barrier layer or transition metalcompound barrier layer for semiconductor device metallization so as toproduce a substantially oxygen-free interface therebetween. In oneembodiment, the method comprises forming the barrier layer on a surfaceof a substrate and subjecting the barrier layer to a process conditionso as to form a removable passivated surface on the barrier layer. Themethod further comprises removing the passivated surface from thebarrier layer and depositing the gapfill copper layer onto the barrierlayer.

Another aspect of the present invention is an integrated system fordepositing a copper layer onto a transition metal barrier layer ortransition metal compound barrier layer for semiconductor devicemetallization so as to produce a substantially oxygen-free interfacetherebetween. In one embodiment, the integrated system comprises atleast one process module configured for barrier layer deposition andpassivated surface formation and at least one other process moduleconfigured for passivated surface removal and deposition of copper ontothe barrier layer. The system further includes at least one transfermodule coupled to the at least one process module and to the at leastone other process module. The at least one transfer module is configuredso that the substrate can be transferred between the modulessubstantially without exposure to an oxide-forming environment.

It is to be understood that the invention is not limited in itsapplication to the details of construction and to the arrangements ofthe components set forth in the following description or illustrated inthe drawings. The invention is capable of other embodiments and of beingpracticed and carried out in various ways. In addition, it is to beunderstood that the phraseology and terminology employed herein are forthe purpose of description and should not be regarded as limiting.

As such, those skilled in the art will appreciate that the conception,upon which this disclosure is based, may readily be utilized as a basisfor the designing of other structures, methods, and systems for carryingout aspects of the present invention. It is important, therefore, thatthe claims be regarded as including such equivalent constructionsinsofar as they do not depart from the spirit and scope of the presentinvention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a process flow diagram of an embodiment of the presentinvention.

FIG. 1A is a process flow diagram of an embodiment of the presentinvention.

FIG. 2 is a diagram of an embodiment of the present invention.

FIG. 3 is a diagram of an embodiment of the present invention.

FIG. 4 is a diagram of an embodiment of the present invention.

FIG. 5 is a diagram of an embodiment of the present invention.

FIG. 6 is a diagram of an embodiment of the present invention.

FIG. 7 is a diagram of an embodiment of the present invention.

Skilled artisans appreciate that elements in the figures are illustratedfor simplicity and clarity and have not necessarily been drawn to scale.For example, the dimensions of some of the elements in the figures maybe exaggerated relative to other elements to help to improveunderstanding embodiments of the present invention.

DESCRIPTION

This invention pertains to methods and systems for fabricatingsemiconductor devices. More specifically, the present invention pertainsto metallization for integrated circuits using barrier layers and metallines. The operation of embodiments of the present invention will bediscussed below, primarily, in the context of transition metal barrierlayers or transition metal compound barrier layers and copper metallines for silicon integrated circuits. However, it is to be understoodthat embodiments in accordance with the present invention may be usedfor other metallization systems for which a substantially oxygen-freeinterface between the barrier layer and metal line is needed.

In the following description of the figures, identical referencenumerals have been used when designating substantially identicalelements or steps that are common to the figures.

For the following description, the term “passivated surface” is definedhere to mean a surface that does not form a substantial amount of oxidecompounds and does not contain a substantial amount of oxygen bound as acomponent of the passivated surface. Furthermore, the passivated surfaceis characterized as being resistant to the transport of oxygen or itotherwise prevents substantial oxidation of materials beneath thepassivated surface for later process steps. It is also to be understoodthat the passivated surface may have a thickness of an atomic monolayerbut is not restricted to a monolayer thickness. For some embodiments ofthe present invention, the passivated surface may be a layer of materialhaving a thickness greater than the thickness of a monolayer.

Reference is now made to FIG. 1 where there is shown a process flowdiagram according to one embodiment of the present invention. Processflow diagram 20 shows a method of depositing a gapfill copper layer ontoa transition metal barrier layer or transition metal compound barrierlayer for integrated circuit metallization so as to produce asubstantially oxygen-free interface between the barrier layer and thecopper layer. Process flow diagram 20 includes step 25, step 30, step35, and step 40. Step includes forming a barrier layer on a surface of asubstrate. Step 30 includes subjecting the barrier layer to at least onecontrolled process condition so as to form a removable passivatedsurface on the barrier layer. Step 35 includes removing the passivatedsurface from the barrier layer. Step 40 includes depositing the gapfillcopper layer onto the barrier layer. Process flow 20 is carried out sothat there is substantially no oxide present between the barrier layerand the gapfill copper layer.

Numerous embodiments of the present invention can be obtained as aresult of selecting various options for carrying out the steps shown inprocess flow diagram 20. Step 25 can be accomplished by one or moreprocesses such as physical vapor deposition, chemical vapor deposition,and atomic layer deposition. A variety of materials or material systemscan be used for the barrier layer formed in step 25. The materialselected for the barrier layer will be a factor influencing theselection of the process used for forming the barrier layer. In apreferred embodiment of the present invention, step 25 involves forminga barrier layer that includes a transition metal or a transition metalcompound. For copper metallization systems, preferred barrier layermaterials for embodiments of the present invention are tantalum,tantalum nitride, or a combination of the two. Tantalum and tantalumnitride can be deposited by physical vapor deposition processes.However, for preferred embodiments of the present invention, step 25 isaccomplished using atomic layer deposition to deposit tantalum nitridebarrier layers.

A further step (not shown in FIG. 1) that is optional for someembodiments of the present invention includes treating the surface ofthe barrier layer after the barrier has been formed. Treating thesurface of the barrier layer may be performed in a variety of ways; thestep is selected so as to prepare the surface of the barrier layer forfollow-on processing steps. Treating the surface of the barrier layer isprimarily directed toward improving the surface adhesion or improvingthe contact resistance for layers deposited on the barrier layer.According to one embodiment of the present invention, treating thesurface of the barrier layer includes subjecting the surface of thebarrier layer to a hydrogen containing plasma. The hydrogen containingplasma may be configured to remove contaminants or other materials onthe surface of the barrier layer such as to decompose metal oxide ormetal nitride formed on the surface of the barrier layer to a metal soas to produce a metal rich surface at the surface of the barrier layer.An example of a suitable hydrogen containing plasma for treating thesurface of the barrier layer is described in commonly owned U.S. patentapplication Ser. No. 11/514,038, filed on Aug. 30, 2006 and isincorporated herein in its entirety by this reference.

As another option, treating the surface of the barrier may includeenriching the surface of the barrier layer with a metal such as bydepositing the metal onto the surface of the barrier layer. A preferredmethod for embodiments of the present invention for treating the surfaceof the barrier includes depositing a metal using a plasma implantationprocess to incorporate the metal with the surface of the barrier layer.Preferably, treating the barrier layer surface is performed either aspart of step 25 or at another point in the process prior to forming theremovable passivated surface on the barrier layer. It is to beunderstood that treating the barrier layer surface is not a requiredstep for all embodiments of the present invention.

According to preferred embodiments of the present invention, the processconditions used for forming the removable passivated surface on thebarrier layer are selected so that the passivated surface issubstantially free of oxygen. This means that the process conditions areselected so that they do not require the use of oxygen or oxygencompounds that can result in the oxidation of the surface of the barrierlayer or incorporation of oxygen into the passivated surface.

A variety of processes and process conditions can be used for step 30 ofprocess flow 20. As options for step 30, atomic layer deposition orphysical vapor deposition can be used to form the passivated surface onthe barrier layer formed in step 25. In one embodiment of the presentinvention, step 30 includes depositing an effective amount of rutheniumto form the passivated surface. The effective amount of rutheniumconstitutes an amount sufficient for substantially preventing oxideformation on or in the underlying barrier layer. The thickness ofruthenium used for preventing oxidation may be about 2-10 monolayers forsome embodiments of the present invention. For other embodiments of thepresent invention, step 30 includes depositing an effective amount of atleast one of the elements cobalt, rhodium, rhenium, osmium, iridium, andmolybdenum to form the passivated surface. Again, the effective amountconstitutes an amount sufficient for substantially preventing oxideformation on or in the underlying barrier layer.

As another option for embodiments of the present invention, step 30 forprocess flow 20 is accomplished by forming a passivated surfacecontaining silicon. More specifically for one embodiment, step 30includes subjecting the barrier layer to a reactive gas containingsilicon so that silicon is available to form the passivated surface.Optionally, step 30 may include a silicidation process in which siliconis deposited onto the surface of a transition metal or transition metalcompound barrier layer. The barrier layer and the silicon are heated aneffective amount so as to form a silicide with the transition metal atthe surface of the barrier layer. As another option, step 30 may includedepositing a metal and silicon onto the barrier layer so as to form asilicide as the passivated surface. In a preferred embodiment of thepresent invention, process flow 20 uses tantalum or tantalum nitride forthe barrier layer and step 30 includes forming a tantalum silicide forthe passivated surface.

As indicated above, embodiments of the present invention are not limitedto a passivated surface formed by depositing a layer of material ontothe barrier layer. Optionally, the passivated surface may be formed by achemical reaction with the surface of the barrier layer to form ahalogen compound at the surface of the barrier layer sufficient toprevent substantial oxide formation on or in the barrier layer.According to one embodiment of the present invention, process step 30 ofprocess flow 20 is accomplished by subjecting the barrier layer to areactive gas containing one or more of the elements fluorine, bromine,and iodine to form the passivated surface. Preferably, the reactive gasis generated from a compound containing one or more of the elementsfluorine, bromine, and iodine. As an option, the reactive gas may begenerated from a glow discharge plasma using a suitable feed gas such asa glow discharge plasma containing one or more of the elements fluorine,bromine, and iodine.

The process of forming the barrier layer as indicated by step 25 andprocess flow 20 can be performed using a process in which anelectrostatic chuck is used to hold the substrate in place during thebarrier deposition step. The generation of the electrostatic forces thathold the substrate is usually referred to as chucking the substrate. Theneutralization of the electrostatic forces so as to release thesubstrate is usually referred to as dechucking. For some processes,dechucking involves running a plasma at suitable process conditions toneutralize the electrostatic forces so that the substrate can bereleased.

Another embodiment of the present invention is a process flow as shownin FIG. 1 in which step 25 uses an electrostatic chuck for holding thesubstrate during formation of the barrier layer and step 30 uses plasmaprocess conditions for forming the passivated surface while alsoproviding conditions for dechucking the substrate. More specifically forsome embodiments of the present invention, step 30 uses reactive gasesin a plasma to form the passivated surface and to provide the chargeneeded to dechuck the substrate. One approach would be to replace one ormore of the gases typically used for dechucking the substrate with oneor more reactive gases for forming the passivated surface. Some examplesof suitable gases are gases containing one or more of the elementsfluorine, bromine, and iodine.

Step 35 includes removing the passivated surface from the barrier layerand can be accomplished by a variety of processes such as dry etchprocesses and such as liquid chemical etch processes. As options, thedry etch processes may be processes such as etching with reactive gasesto remove the passivated surface and such as plasma enhanced etchprocesses. Examples of liquid etch processes are etching with acidsolutions, etching with base solutions, and removal with solvents. For apreferred embodiment of the present invention, the passivated surface isselected to have properties so that it is removed by solutions used forelectroless copper deposition. In other words, a preferred embodiment ofthe present invention includes removing the passivated surface as partof an electroless copper deposition process.

More preferably, the passivated surface has properties so as to havesome survivability during electroless copper deposition using aqueoussolutions. This means that it is preferable for the passivated surfaceto remain intact to protect the barrier layer from oxidation and thepassivated surface is removed in situ during electroless copper plating.

A variety of processes and process conditions can be used for performingstep 40. As an option for step 40, electroless deposition can be used todeposit the gapfill copper layer onto the barrier layer formed in step25. In a more preferred embodiment, step 40 includes using electrolessdeposition to deposit a copper seed layer followed by an electroplatedcopper gapfill layer. Electroless copper deposition and electrochemicalplating process are well-known wet processes.

In yet another embodiment of the present invention, process flow 20further comprises at least one of storing the substrate with passivatedsurface on the barrier layer for an amount of time and transporting thesubstrate to a preparation module for preparing the substrate fordepositing the gapfill copper layer. This embodiment of the presentinvention is suitable for a passivated surface that is capable ofprotecting the underlying barrier layer from oxide formation duringtransport or during storage under environmental conditions other thanthose in a vacuum transfer module or controlled environment transfermodule. More particularly, this embodiment of the present invention usesa passivated surface that can prevent substantial oxide formation of theunderlying barrier layer for extended periods of time or exposure toprocess conditions that may or may not cause oxide formation in theabsence of the passivated surface. One embodiment of the presentinvention includes process flow 20 in which the passivated surface isconfigured to prevent substantial oxide formation on the barrier layerwhen transporting or storing the barrier layer with the passivatedsurface in an oxygen containing environment.

According to another embodiment of the present invention, process step30 includes forming a passivated surface on the barrier layer that hasautocatalytic properties for electroless deposition of copper. Morespecifically, the passivated surface formed in step 30 has propertiesthat protect the underlying barrier layer from oxide formation. Thepassivated surface also has properties that catalyze electrolessdeposition of copper. In one embodiment of the present invention, thepassivated surface participates in a displacement reaction where copperin the electroless deposition solution displaces the material of thepassivated surface.

It is to be understood that step 35 is an optional step for someembodiments of the present invention. In other words, another embodimentof the present invention is the process flow shown in FIG. 1A thatincludes step 25, step 31, and step 40; step 35 is not used.Specifically, the passivated surface is not removed and remains anintegral component of the barrier and copper interconnect materialduring electroless copper plating or other copper deposition processes.Step 25 is essentially the same as described for the process flow inFIG. 1. Step 31 is essentially the same as step 30 with the exceptionthat the passivated surface does not need to be removable in follow-onprocesses. Step 41 is essentially the same as step 40 with the exceptionthat copper is deposited on to the passivated surface.

Reference is now made to FIG. 2 where there is shown a schematic diagramof an exemplary integrated system 50, according to one embodiment of thepresent invention, for depositing a copper layer onto a transition metalbarrier layer or transition metal compound barrier layer on substratesfor integrated circuit metallization. Integrated system 50 is configuredso as to produce a substantially oxygen-free interface between thebarrier layer and the copper layer. A preferred embodiment of integratedsystem 50 is configured to substantially perform the steps of processflow 20 and variations thereof.

For the embodiment shown in FIG. 2, integrated system 50 comprises atleast one transfer module 52, a barrier deposition module 58, apassivated surface formation module 60, a passivated surface removalmodule 63, and a copper gapfill module 65. Integrated system 50 isconfigured so that it allows minimal exposure of the substrate surfaceto oxygen at critical steps for which oxide formation is undesirable. Inaddition, since it is an integrated system, the substrate can betransferred from one process module immediately to the next station,which limits the duration of exposure to oxygen.

According to one embodiment of the present invention, integrated system50 is configured to process substrate(s) through the entire processsequence of process flow 20 of FIG. 1 and variations thereof. Morespecifically, barrier deposition module 58 is configured to form abarrier layer on a substrate. Preferably, barrier deposition module 58is configured to deposit a barrier layer material such as tantalum,tantalum nitride, and combinations of the two. As an option, barrierdeposition module 58 can be configured for physical vapor deposition ofthe barrier layer or atomic layer deposition of the barrier layer. In apreferred embodiment, barrier deposition module 58 is configured foratomic layer deposition. In one possible configuration, barrierdeposition module 58 is configured for an atomic layer depositionprocess operated at less than 1 Torr. As another option, barrierdeposition module 58 is configured for atomic layer deposition for ahigh-pressure process using supercritical CO2 and organometallicprecursors to form the barrier layer. In yet another configuration,barrier deposition module 58 is configured for a physical vapordeposition process operating at pressures less than 1 Torr. Details ofan exemplary reactor for a high pressure process using supercritical CO2is described in commonly assigned application Ser. No. 10/357,664,titled “Method and Apparatus for Semiconductor Wafer Cleaning UsingHigh-Frequency Acoustic Energy with Supercritical Fluid”, filed on Feb.3, 2003, which is incorporated herein by this reference. Once thebarrier layer is formed, the substrate should be transferred in acontrolled-ambient environment to limit exposure to oxygen; this isaccomplished with transfer module 52.

Passivated surface formation module 60 is configured to form apassivated surface, as defined above, on the barrier layer. Passivatedsurface formation module 60 can be implemented in a wide variety ofconfigurations for forming the passivated surface. In one configuration,passivated surface formation module 60 is configured to subject thebarrier layer to a reactive gas mixture containing one or more of theelements fluorine, bromine, and iodine so as to form a halide compoundon the barrier layer sufficient to prevent oxidation of the underlyingbarrier layer. As a further option, passivated surface formation module60 is configured to generate a plasma in a gas containing one or more ofthe elements fluorine, bromine, and iodine for forming the passivatedsurface.

Optionally, passivated surface formation module 60 is configured tosubject the barrier layer to a reactive gas containing silicon so as todeposit a thin layer of silicon on the barrier layer. In anotherembodiment, passivated surface formation module 60 is configured tosubject the barrier layer to a reactive gas containing silicon andheating the substrate an effective amount so as to form a silicide withthe transition metal at the surface of the barrier layer. Passivatedsurface formation module 60 may be configured for other types ofsilicidation processes to form the passivated surface. As anotheroption, passivated surface formation module 60 is configured to deposita metal and silicon onto the barrier layer so as to form a silicide. Fora preferred embodiment, passivated surface formation module 60 isconfigured for atomic layer deposition of an effective amount of atleast one of cobalt, rhodium, rhenium, osmium, iridium, and molybdenumto substantially prevent oxidation of the underlying barrier layer. Moreparticularly, the passivated surface formation module comprises anatomic layer deposition module, a silicon deposition module, or asilicidation module for some embodiments of the present invention.

According to one embodiment of the present invention, passivated surfaceformation module 60 is a deposition module. Examples of suitable typesof the deposition module are chemical vapor deposition module, atomiclayer deposition module, plasma enhanced chemical vapor depositionmodule, and physical vapor deposition module. The deposition moduledeposits the material of the passivated surface onto the surface of thebarrier layer.

According to another embodiment of the present invention, passivatedsurface formation module is a chemical reactor that causes a chemicalreaction with the surface of the barrier layer. The product of thechemical reaction forms the passivated surface.

Passivated surface removal module 63 is configured to remove thepassivated surface from the barrier layer. Passivated surface removalmodule 63 can be implemented in a variety of configurations. Forspecific embodiments of the present invention, the configuration ofpassivated surface removal module 63 will depend on the type ofpassivated surface to be removed.

As one option, passivated surface removal module 63 is a dry etch modulethat uses reactive gases to remove the passivated surface or a plasmaetch module such as a module configured for plasma enhanced etchprocesses. As another option, passivated surface removal module 63 is aliquid etch module that uses processes such as etching with acidsolutions, etching with base solutions, and removal with solvents. For apreferred embodiment of the present invention, passivated surfaceremoval module 63 is configured so that its processes are compatiblewith the follow-on processes for depositing copper.

According to a preferred embodiment of the present invention, theproperties of the passivated surface are selected so that the passivatedsurface has some amount of survivability so as to provide someprotection from oxidation during an electroless copper depositionprocess. More specifically, this means that the passivated surface isselected so that it is removed during the electroless copper depositionprocess. As an option, the passivated surface is removed from thebarrier layer as copper is deposited on the surface of the barrierlayer. An additional option includes leaving the passivated surfaceintact and depositing the copper layer directly on the passivatedsurface.

Copper gapfill module 65 is configured to deposit a gapfill copperlayer. Optionally, copper gapfill module 65 can be configured to depositthe gapfill copper layer using electroless deposition, electrochemicalplating, or electroless deposition and electrochemical plating. Morespecifically, copper gapfill module 65 may be configured to deposit aconformal copper seed layer on the barrier surface, followed by a thickcopper gapfill (or bulk fill) process. In one embodiment, copper gapfillmodule 65 is configured to perform an electroless process to produce aconformal copper seed layer. Copper gapfill module 65 can be furtherconfigured for a thick copper bulk fill process by an electrolessdeposition process or an electrochemical plating process. Electrolesscopper deposition and electrochemical plating process are well-known wetprocesses. For a wet process to be integrated in a system withcontrolled processing and transporting environment, the reactor needs tobe integrated with a rinse/dryer to enable dry-in/dry-out processcapability. In addition, the system needs to be filled with inert gas toensure minimal exposure of the substrate to oxygen. Recently, adry-in/dry-out electroless copper process has been developed. Further,all fluids used in the process are de-gassed, i.e. dissolved oxygen isremoved by commercially available degassing systems.

The environment for electroless deposition also needs to be controlledto provide low (or limited) levels of oxygen and moisture (water vapor).Inert gas can also be used in copper gapfill module 65 to ensure lowlevels of oxygen are in the processing environment. Copper gapfillmodule 65 can be configured to perform the electroless depositionprocess in a number of ways, such as puddle-plating, where fluid isdispensed onto a substrate and allowed to react in a static mode, afterwhich the reactants are removed and discarded, or reclaimed. In anotherembodiment, copper gapfill module 65 includes a proximity process headto limit the electroless process liquid so that it is only in contactwith the substrate surface on a limited region. The substrate surfacethat is not under the proximity process head is dry. Details of such aprocess and system can be found in U.S. application Ser. No. 10/607,611,titled “Apparatus And Method For Depositing And Planarizing Thin FilmsOf Semiconductor Wafers,” filed on Jun. 27, 2003, and U.S. applicationSer. No. 10/879,263, titled “Method and Apparatus For PlatingSemiconductor Wafers,” filed on Jun. 28, 2004, both of which areincorporated herein in their entireties.

The at least one transfer module 52 is configured for vacuum transfer ofthe substrate or controlled environment transfer of the substrate.Alternatively, the at least one transfer module 52 may comprise twotransfer modules with one transfer module configured for vacuum transferand a second transfer module configured for controlled environmenttransfer. Transfer module 52 is coupled to barrier deposition module 58,passivated surface formation module 60, passivated surface removalmodule 63, and copper gapfill module 65. Transfer module 52 isconfigured so that the substrate can be transferred between the modulessubstantially without exposure to an oxygen-containing environment or anoxide-forming environment.

Wet processes such as those performed in copper gapfill module 65 andsuch as those that may be performed in passivated surface removal module63 are typically operated near atmospheric pressure, while the dryprocesses such as those performed in barrier deposition module 58,passivated surface formation module 60, and possibly passivated surfaceremoval module 63 are usually operated at less than 1 Torr. Therefore,integrated system 50 needs to be able to handle a mixture of dry and wetprocesses. The least at one transfer module 52 is equipped with one ormore robots to move the substrate from one process area to anotherprocess area. The process area could be a substrate cassette, a reactor,or a loadlock (cassette and loadlock not shown in FIG. 2).

As described above, it is important to control the processing andtransport environments to minimize the exposure of the barrier layersurface to oxygen prior to forming the passivated surface so as to avoidformation of an oxide on the barrier layer. The substrate should beprocessed under a controlled environment, where the environment iseither under vacuum or filled with one or more inert gas(es) to limitthe exposure of the substrate to oxygen. To provide a controlledenvironment for substrate transfer, transfer module 52 is configured sothat the environment is controlled to be free of oxygen. In oneexemplary configuration, transfer module 52 is configured to have inertgas(es) fill the transfer module during substrate transfer.Additionally, all fluids used in the process are de-gassed, i.e.dissolved oxygen is removed by commercially available degassing systems.Exemplary inert gas includes nitrogen (N2), helium (He), neon (Ne),argon (Ar), krypton (Kr), and xenon (Xe).

Reference is now made to FIG. 3 where there is shown a schematic diagramof an exemplary integrated system 100, according to another embodimentof the present invention, for depositing a copper layer onto atransition metal barrier layer or transition metal compound barrierlayer on substrates for integrated circuit metallization. Integratedsystem 100 is configured so as to produce a substantially oxygen-freeinterface between the barrier layer and the copper layer. A preferredembodiment of integrated system 100 is configured to perform the stepsof process flow 20 and variations thereof.

Integrated system 100 comprises a vacuum transfer module 105 connectedwith a barrier deposition module 108, a loadlock 110, a barriertreatment module 113, and a passivated surface formation module 115.Integrated system 100 also includes a controlled environment transfermodule 120 connected with a passivated surface removal module 125, acopper seed deposition module 128, and a copper gapfill module 130. Asecond loadlock 123 is included in integrated system 100 for joiningvacuum transfer module 105 and control environment transfer module 120.

For integrated system 100, barrier deposition module 108 is configuredso as to have essentially the same structure as described above forbarrier deposition module 58; passivated surface formation module 115 isconfigured so as to have essentially the same structure as describedabove for passivated surface formation module 60. Loadlock 110 isprovided to allow substrate transfer for vacuum transfer module 105while maintaining vacuum conditions for vacuum transfer module 105.

Barrier treatment module 113 is configured to treat the surface of thebarrier layer after formation of the barrier layer. More specifically,barrier treatment module 113 is configured so as to prepare the surfaceof the barrier layer for follow-on processing steps. Primarily, barriertreatment module 113 is configured to produce an improvement of surfaceproperties for the barrier layer such as to obtain improved surfaceadhesion and such as to improve the contact resistance for layersdeposited on the barrier layer. According to one embodiment of thepresent invention, barrier treatment module 113 includes a plasmachamber configured to subject the surface of the barrier layer to ahydrogen containing plasma so as to remove contaminants on the surfaceof the barrier layer or decomposed metal oxides formed on the surface ofthe barrier layer so as to produce a metal rich surface at the surfaceof the barrier layer.

As another option, barrier treatment module 113 is configured to enrichthe surface of the barrier layer with a metal such as by depositing themetal onto the surface of the barrier layer. In a preferredconfiguration, barrier treatment module 113 includes a plasma chamberconfigured for plasma implantation of a metal. The implanted metal isincorporated with the surface of the barrier layer to produce a metalrich surface for the barrier layer.

Vacuum transfer module 105 is configured for operation under vacuum (<1Torr). Controlled environment transfer module 120 is configured foroperation at around 1 atmosphere pressure. Loadlock 123 is placedbetween vacuum transfer module 105 and controlled environment transfermodule 125 to allow substrate transfer between the two modules operatedunder different pressures while preserving the integrity of theenvironments in each transfer module. Loadlock 123 is configured to beoperated under vacuum at a pressure less than 1 Torr, or at lab ambient,or to be filled with an inert gas selected form a group of inert gases.

Passivated surface removal module 125 is configured to remove of thepassivated surface formed in passivated surface formation module 115.Passivated surface removal module 125 is preferably configured to removethe passivated surface using processes that operate at about atmosphericpressure such as removal processes that use liquid chemicals forremoving the passivated surface. In one embodiment words, passivatedsurface removal module 125 comprises a liquid etch process moduleconfigured to perform liquid etch processes such as etching with acidsolutions, etching with base solutions, and removal with solvents. For amore preferred embodiment of the present invention, passivated surfaceremoval module 63 is configured so that its processes are compatiblewith the follow-on processes for depositing copper.

Copper seed deposition module 128 is configured to deposit a conformalcopper seed layer on the barrier surface. Preferably, copper seeddeposition module 128 is configured to perform an electroless process toproduce the copper seed layer. Copper gapfill module 130 is configuredfor a thick copper bulk fill process by an electroless depositionprocess or an electrochemical plating process. As stated above,electroless copper deposition and electrochemical plating are well-knownwet processes. For a wet process to be integrated in a system withcontrolled processing and transporting environment, the reactor needs tobe integrated with a rinse/dryer to enable dry-in/dry-out processcapability. In addition, the system needs to be filled with inert gas toensure minimal exposure of the substrate to oxygen. Recently, adry-in/dry-out electroless copper process has been developed. Further,all fluids used in the process are de-gassed, i.e. dissolved oxygen isremoved by commercially available degassing systems.

Wet processes such as those performed in passivated surface removalmodule 125, copper seed deposition module 128, and copper gapfill module130 are typically operated near atmospheric pressure, while the dryprocesses such as those performed in barrier deposition module 108,passivated surface formation module 115, and barrier clean module 113are usually operated at less than 1 Torr. Therefore, integrated system50 needs to be able to handle a mixture of dry and wet processes. Vacuumtransfer module 105 and controlled environment transfer module 120 areequipped with one or more robots to move the substrate from one processarea to another process area. The process area could be a substratecassette, a reactor, or a loadlock (cassette and loadlock not shown inFIG. 3).

Reference is now made to FIG. 4 where there is shown a schematic diagramof an exemplary integrated system 150 according to another embodiment ofthe present invention for depositing a copper layer onto a transitionmetal barrier layer or transition metal compound barrier layer onsubstrates for integrated circuit metallization. Integrated system 150is configured so as to produce a substantially oxygen-free interfacebetween the barrier layer and the copper layer. A preferred embodimentof integrated system 150 is configured to substantially perform thesteps of process flow 20 and variations thereof.

Integrated system 150 comprises a vacuum transfer module 105 connectedwith a barrier deposition module 108, a loadlock 110, a barriertreatment module 113, and a passivated surface formation module 115A.Integrated system 150 also includes a controlled environment transfermodule 120 connected with a copper seed deposition module 128, and acopper gapfill module 130. A second loadlock 123 is included inintegrated system 150 for joining vacuum transfer module 105 andcontrolled environment transfer module 120.

Integrated system 150 is essentially the same as integrated system 100described for FIG. 3 with the exception that integrated system 150 isconfigured so that passivated surface formation module 115A forms apassivated surface that is removed in situ during electroless copperdeposition. In other words, the passivated surface has somesurvivability in aqueous solutions used for electroless copperdeposition. The passivated surface is removed in copper seed depositionmodule 128 or copper gapfill module 130 as part of or in preparation forcopper seed deposition or copper gapfill. More specifically, integratedsystem 150 includes copper seed deposition module 128 configured forpassivated surface removal and for copper seed deposition. Optionally,the passivated surface is retained in copper seed deposition module 128or copper gapfill module 130 as part of copper seed deposition or coppergapfill.

Reference is now made to FIG. 5 where there is shown a schematic diagramof an exemplary integrated system 175, according to another embodimentof the present invention, for depositing a copper layer onto atransition metal barrier layer or transition metal compound barrierlayer on substrates for integrated circuit metallization. Integratedsystem 175 is configured so as to produce a substantially oxygen-freeinterface between the barrier layer and the copper layer. A preferredembodiment of integrated system 175 is configured to substantiallyperform the steps of process flow 20 and variations thereof.

Integrated system 175 comprises a vacuum transfer module 105 connectedwith a barrier deposition and passivated surface formation module 108Aand a loadlock 110. Integrated system 175 also includes a controlledenvironment transfer module 120 connected with a passivated surfaceremoval module 125, a copper seed deposition module 128, and a coppergapfill module 130. A second loadlock 123 is included in integratedsystem 100 for joining vacuum transfer module 105 and controlenvironment transfer module 120.

Integrated system 175 is essentially the same as integrated system 100described for FIG. 3 with the exception that integrated system 175 isconfigured so that module 108A forms a barrier layer and also forms apassivated surface on the barrier layer. Furthermore, integrated system175 does not require a separate module for treating the barrier layerfor some applications. Integrated system 175 is configured so that thepassivated surface is removed in passivated surface removal module 125.

Reference is now made to FIG. 6 where there is shown a schematic diagramof an exemplary integrated system 200 according to another embodiment ofthe present invention for depositing a copper layer onto a transitionmetal barrier layer or transition metal compound barrier layer onsubstrates for integrated circuit metallization. Integrated system 200is configured so as to produce a substantially oxygen-free interfacebetween the barrier layer and the copper layer. A preferred embodimentof integrated system 200 is configured to substantially perform thesteps of process flow 20 and variations thereof.

Integrated system 200 comprises a vacuum transfer module 105 connectedwith a barrier deposition and passivated surface formation module 108Band a loadlock 110. Integrated system 200 also includes a controlledenvironment transfer module 120 connected with a copper seed depositionmodule 128 and a copper gapfill module 130. A second loadlock 123 isincluded in integrated system 150 for joining vacuum transfer module 105and control environment transfer module 120.

Integrated system 200 is essentially the same as integrated system 150described for FIG. 4 with the exception that integrated system 200 isconfigured so that module 108B forms a barrier layer and also forms apassivated surface on the barrier layer that is removable in situ duringelectroless copper deposition. The passivated surface is removed incopper seed deposition module 128 or copper gapfill module 130 as partof or in preparation for copper seed deposition. More specifically,integrated system 200 includes copper seed deposition module 128configured for passivated surface removal and for copper seeddeposition.

Reference is now made to FIG. 7 where there is shown a schematic diagramof an exemplary integrated system 225, according to another embodimentof the present invention, for depositing a copper layer onto atransition metal barrier layer or transition metal compound barrierlayer on substrates for integrated circuit metallization. Integratedsystem 225 is configured so as to produce a substantially oxygen-freeinterface between the barrier layer and the copper layer. A preferredembodiment of integrated system 225 is configured to perform the stepsof process flow 20 and variations thereof.

Integrated system 225 comprises a vacuum transfer module 105 connectedwith a barrier deposition and passivated surface formation module 108Band a loadlock 110. Integrated system 225 also includes a controlledenvironment transfer module 120 connected with a passivated surfaceremoval and copper gapfill module 132. A second loadlock 123 is includedin integrated system 150 for joining vacuum transfer module 105 andcontrolled environment transfer module 120.

Integrated system 225 is essentially the same as integrated system 200described for FIG. 6 with the exception that integrated system 225 isconfigured so that passivated surface removal and copper gapfill module132 removes the passivated surface and deposits the copper gapfilllayer. In one embodiment, module 132 is configured to use an electrolesscopper deposition process for which the passivated surface formed inmodule 108B is removed in situ during electroless copper deposition. Thepassivated surface is removed in module 132 as part of or in preparationfor copper seed deposition or copper gapfill.

Another embodiment of the present invention is a system for depositing acopper layer onto a transition metal barrier layer or transition metalcompound barrier layer for integrated circuit metallization. The systemcomprises a barrier deposition and passivated surface formation moduleconfigured to form a barrier layer on a substrate and configured to forma passivated surface on the barrier layer. The system further comprisesa passivated surface removal and copper deposition module configured toremove the passivated surface from the barrier layer and configured todeposit a copper layer onto the barrier layer. The barrier deposition inpassivated surface formation module and the passivated surface removaland copper deposition module are disposed so that substrates processedin the barrier deposition and passivated surface formation module can beprocessed in the passivated surface removal and copper deposition moduleafter at least one of exposure to an oxygen containing environment,storage for an amount of time, and storage in an oxygen-free environmentfor an amount of time. The system for this embodiment does not require atransfer module connecting the barrier deposition in passivated surfaceformation module and the passivated surface removal and copperdeposition module.

In the foregoing specification, the invention has been described withreference to specific embodiments. However, one of ordinary skill in theart appreciates that various modifications and changes can be madewithout departing from the scope of the present invention as set forthin the claims below. Accordingly, the specification and figures are tobe regarded in an illustrative rather than a restrictive sense, and allsuch modifications are intended to be included within the scope of thepresent invention.

Benefits, other advantages, and solutions to problems have beendescribed above with regard to specific embodiments. However, thebenefits, advantages, solutions to problems, and any element(s) that maycause any benefit, advantage, or solution to occur or become morepronounced are not to be construed as a critical, required, or essentialfeature or element of any or all the claims.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having,” “at least one of,” or any other variationthereof, are intended to cover a non-exclusive inclusion. For example, aprocess, method, article, or apparatus that comprises a list of elementsis not necessarily limited only to those elements but may include otherelements not expressly listed or inherent to such process, method,article, or apparatus. Further, unless expressly stated to the contrary,“or” refers to an inclusive or and not to an exclusive or. For example,a condition A or B is satisfied by any one of the following: A is true(or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

Further, unless expressly stated to the contrary, “at least one of” isto be interpreted to mean “one or more.” For example, a process, method,article, or apparatus that comprises one or more of a list of elementsand if one or more of the elements comprises a sub-list of sub-elements,then the sub-elements are to be considered in the same manner as theelements. For example, at least one of A and B is satisfied by any oneof the following: A is true (or present) and B is false (or notpresent), A is false (or not present) and B is true (or present), andboth A and B are true (or present).

1. A method of depositing a gapfill copper layer onto a transition metalbarrier layer or transition metal compound barrier layer for integratedcircuit metallization so as to produce a substantially oxygen-freeinterface there between, the method comprising: (a) forming the barrierlayer on a surface of a substrate; (b) forming a removable passivatedsurface on the barrier layer; (c) removing the passivated surface fromthe barrier layer; and (d) depositing the gapfill copper layer onto thebarrier layer.
 2. The method of claim 1, further comprising at least oneof:
 1. storing the substrate with the passivated surface on the barrierlayer for an amount of time and
 2. transporting the substrate with thepassivated surface on the barrier layer.
 3. The method of claim 1,wherein the passivated surface is substantially free of oxygen.
 4. Themethod of claim 1, further comprising at least one of:
 1. storing thesubstrate with the passivated surface on the barrier layer in anoxygen-containing environment for an amount of time and
 2. transportingthe substrate with the passivated surface on the barrier layer in anoxygen-containing environment.
 5. The method of claim 1, furthercomprising at least one of:
 1. storing the substrate with the passivatedsurface on the barrier layer in a substantially non-oxygen containingenvironment for an amount of time and
 2. transporting the substrate withthe passivated surface on the barrier layer in a substantiallynon-oxygen containing environment.
 6. The method of claim 1, whereinremoving the passivated surface occurs as part of depositing the gapfillcopper layer onto the barrier layer.
 7. The method of claim 1, whereinforming the removable passivated surface includes treating the barrierlayer surface in a hydrogen containing plasma so as to clean the barrierlayer surface of oxide.
 8. The method of claim 1, wherein forming theremovable passivated surface includes enriching the surface of thebarrier layer with a transition metal.
 9. The method of claim 1, whereinforming the removable passivated surface is accomplished by atomic layerdeposition.
 10. The method of claim 1, wherein the barrier layercomprises tantalum or tantalum nitride.
 11. The method of claim 1,wherein forming the removable passivated surface is accomplished bysubjecting the barrier layer to a reactive gas containing at least oneof the elements fluorine, bromine, and iodine.
 12. The method of claim1, wherein forming the removable passivated surface is accomplished bysubjecting the barrier layer to a reactive gas generated from a compoundcontaining at least one of the elements fluorine, bromine, and iodine.13. The method of claim 1, wherein forming the removable passivatedsurface is accomplished by subjecting the barrier layer to a glowdischarge containing at least one of the elements fluorine, bromine, andiodine.
 14. The method of claim 1, wherein forming the removablepassivated surface is accomplished by subjecting the barrier layer to areactive gas containing silicon.
 15. The method of claim 1, whereinforming the removable passivated surface is accomplished by subjectingthe barrier layer to a reactive gas containing silicon and heating thesubstrate an effective amount so as to form a silicide with thetransition metal at the surface of the barrier layer.
 16. The method ofclaim 1, wherein forming the removable passivated surface isaccomplished by silicidation of the barrier layer surface.
 17. Themethod of claim 1, wherein forming the removable passivated surface isaccomplished by depositing a metal and silicon onto the barrier layer soas to form a silicide.
 18. The method of claim 1, wherein forming theremovable passivated surface is accomplished by atomic layer depositionof an effective amount of ruthenium.
 19. The method of claim 1, whereinforming the removable passivated surface is accomplished by depositionof an effective amount of least one of cobalt, rhodium, rhenium, osmium,iridium, and molybdenum.
 20. The method of claim 1, wherein forming theremovable passivated surface is accomplished during a dechucking processfor forming the barrier layer.
 21. The method of claim 1, wherein thepassivated surface has survivability in aqueous electroless copperdeposition solution.
 22. The method of claim 1, wherein removing thepassivated surface is accomplished using a plasma etch process.
 23. Themethod of claim 1, wherein removing the passivated surface isaccomplished using a liquid chemical etch process.
 24. The method ofclaim 1, wherein removing the passivated surface is accomplished usingan electroless plating solution.
 25. An integrated system for depositinga copper layer onto a transition metal barrier layer or transition metalcompound barrier layer for integrated circuit metallization so as toproduce a substantially oxygen-free interface therebetween, theintegrated system comprising: a barrier deposition module configured toform a barrier layer on a substrate; a passivated surface formationmodule configured to form a passivated surface on the barrier layer; apassivated surface removal module configured to remove the passivatedsurface from the barrier layer; a copper gapfill module configured todeposit a gapfill copper layer; and at least one transfer moduleconfigured for vacuum transfer of the substrate or controlledenvironment transfer of the substrate, the least one transfer modulebeing coupled to the barrier deposition module, the passivated surfaceformation module, the passivated surface removal module, and the coppergapfill module and configured so that the substrate can be transferredbetween the modules substantially without exposure to an oxygencontaining environment.
 26. The system of claim 25, wherein the barrierdeposition module is configured to deposit tantalum or tantalum nitride.27. The system of claim 25, wherein the passivated surface formationmodule is configured to: subject the barrier layer to a reactive gasmixture containing at least one of the elements fluorine, bromine, andiodine; subject the barrier layer to a reactive gas containing silicon;subject the barrier layer to a reactive gas containing silicon andheating the substrate an effective amount so as to form a silicide withthe transition metal at the surface of the barrier layer; deposit ametal and silicon onto the barrier layer so as to form a suicide; ordeposit an effective amount of least one of cobalt, rhodium, rhenium,osmium, iridium, and molybdenum by atomic layer deposition.
 28. Thesystem of claim 25, wherein the passivated surface removal modulecomprises a plasma etch module or a liquid chemical etch module.
 29. Thesystem of claim 25, wherein the copper gapfill module comprises at leastone of: an electroless deposition module and an electrochemical platingmodule.
 30. The system of claim 25, wherein the passivated surfaceformation module comprises an atomic layer deposition module, a silicondeposition module, or a silicidation module.
 31. An integrated systemfor depositing a gapfill copper layer onto a transition metal barrierlayer or transition metal compound barrier layer for integrated circuitmetallization so as to produce a substantially oxygen-free interfacetherebetween, the integrated system comprising: a barrier depositionmodule configured to form a barrier layer on a substrate; a passivatedsurface formation module configured to form a passivated surface on thebarrier layer; a passivated surface removal and copper deposition moduleconfigured to remove the passivated surface from the barrier layer andto deposit the copper layer onto the barrier layer; and at least onetransfer module configured for vacuum transfer of the substrate orcontrolled environment transfer of the substrate, the least one transfermodule being coupled to the barrier deposition module, the passivatedsurface formation module, and the passivated surface removal and copperdeposition module so that the substrate can be transferred between themodules substantially without exposure to an oxygen-containingenvironment.
 32. The system of claim 31, wherein the passivated surfaceformation module is configured to form a passivated surface that isremovable in an electroless copper deposition process and the passivatedsurface removal and copper deposition module is configured forelectroless copper deposition or electroless copper deposition andelectrochemical copper plating.
 33. The system of claim 31, wherein thepassivated surface removal and copper deposition module is configured todeposit copper by at least one of electroless copper deposition andelectrochemical copper plating.
 34. The system of claim 31, wherein thebarrier deposition module comprises a tantalum deposition module or atantalum nitride deposition module.
 35. The system of claim 31, whereinthe passivated surface formation module is configured to: subject thebarrier layer to a reactive gas mixture containing at least one of theelements fluorine, bromine, and iodine; subject the barrier layer to areactive gas containing silicon; subject the barrier layer to a reactivegas containing silicon and heating the substrate an effective amount soas to form a silicide with the transition metal at the surface of thebarrier layer; deposit a metal and silicon onto the barrier layer so asto form a silicide; and deposit an effective amount of least one ofcobalt, rhodium, rhenium, osmium, iridium, and molybdenum by atomiclayer deposition.
 36. The system of claim 31, wherein the passivatedsurface formation module comprises an atomic layer deposition module, asilicon deposition module, or a silicidation module.
 37. An integratedsystem for depositing a copper layer onto a transition metal barrierlayer or transition metal compound barrier layer for integrated circuitmetallization so as to produce a substantially oxygen-free interfacetherebetween, the integrated system comprising: a barrier deposition andpassivated surface formation module configured to form a barrier layeron a substrate and configured for forming a passivated surface on thebarrier layer; a passivated surface removal and copper deposition moduleconfigured to remove the passivated surface from the barrier layer andto deposit a copper layer onto the barrier layer; and at least one of avacuum transfer module and a controlled environment transfer modulecoupled to the barrier deposition and passivated surface formationmodule and the passivated surface removal and copper deposition moduleand configured so that the substrate can be transferred between themodules substantially without exposure to an oxide-forming environment.38. The system of claim 37, wherein the passivated surface is removablein an electroless copper deposition process and the passivated surfaceremoval and copper deposition module is configured to deposit copper byelectroless copper deposition or electroless copper deposition andelectrochemical copper plating.
 39. The system of claim 37, wherein thebarrier deposition and passivated surface formation module is configuredto deposit tantalum nitride by atomic layer deposition and to form apassivated surface on the tantalum nitride, the passivated surface isautocatalytic for electroless copper deposition; and the passivatedsurface removal and copper deposition module is configured to depositcopper by electroless copper deposition or electroless copper depositionand electrochemical copper plating.
 40. A system for depositing a copperlayer onto a transition metal barrier layer or transition metal compoundbarrier layer for integrated circuit metallization so as to produce asubstantially oxygen-free interface therebetween, the integrated systemcomprising: barrier deposition and passivated surface formation a moduleconfigured for forming a barrier layer on a substrate and configured forforming a passivated surface on the barrier layer; and a passivatedsurface removal and copper deposition module configured for removing thepassivated surface from the barrier layer and configured for depositinga copper layer onto the barrier layer, wherein the first process moduleand the passivated surface removal and copper deposition module aredisposed so that substrates processed in the barrier deposition andpassivated surface formation module can be processed in the passivatedsurface removal and copper deposition module after at least one of: 1.exposure to an oxygen containing environment,
 2. storage for an amountof time, and
 3. storage in an oxygen-free environment for an amount oftime.
 41. A method of depositing a gapfill copper layer onto atransition metal barrier layer or transition metal compound barrierlayer for integrated circuit metallization so as to produce asubstantially oxygen-free interface there between, the methodcomprising: (a) forming the barrier layer on a surface of a substrate;(b) forming a passivated surface on the barrier layer; and (c)depositing the gapfill copper layer onto the passivated surface.